Formation process of zirconia nanotubes and porous structures and model of oxygen bubble growth

Abstract

Preparation and growth mechanism of anodization of Ti and Al has been widely concerned for two decades, but the research on anodic ZrO2 is relatively lacking. In this paper, anodic TiO2 and ZrO2 nanotubes were prepared in glycerol electrolyte containing 0.35 M NH4F and 4 vol% H2O under different anodizing voltages. We had successfully prepared the anodic ZrO2 nanotubes (AZNTs) with a complete top and a “bulb” at the bottom under 60 V, and with the increase of the applied anodizing voltage, the “bulb” cavity also increased. However, under the same anodizing conditions, the surface of anodic TiO2 nanotubes (ATNTs) is a cluster of nano-tip morphology, and the bottom of the ATNTs is a conventional hemisphere shape. In addition, both AZNTs and porous anodic zirconia (PAZ) were found to coexist in the anodic ZrO2 layer prepared at 60 V. Here, we used the oxygen bubble model and ionic current and electronic current theories to analyze the reason of the special morphology. It is confirmed that the porous anodic oxides are actually evolved from nanotubes. In other words, the structure is essentially the same.